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Review
. 2019 Aug 16;14(16):2760-2769.
doi: 10.1002/asia.201900717. Epub 2019 Jul 19.

The Nature of Hydrogen Bonds: A Delineation of the Role of Different Energy Components on Hydrogen Bond Strengths and Lengths

Stephanie C C van der Lubbe  1 , Célia Fonseca Guerra  1   2
Affiliations
Review

The Nature of Hydrogen Bonds: A Delineation of the Role of Different Energy Components on Hydrogen Bond Strengths and Lengths

Stephanie C C van der Lubbe et al. Chem Asian J. .

Abstract

Hydrogen bonds are a complex interplay between different energy components, and their nature is still subject of an ongoing debate. In this minireview, we therefore provide an overview of the different perspectives on hydrogen bonding. This will be done by discussing the following individual energy components: 1) electrostatic interactions, 2) charge-transfer interactions, 3) π-resonance assistance, 4) steric repulsion, 5) cooperative effects, 6) dispersion interactions and 7) secondary electrostatic interactions. We demonstrate how these energetic factors are essential in a correct description of the hydrogen bond, and discuss several examples of systems whose energetic and geometrical features are not captured by easy-to-use predictive models.

Keywords: cooperative effects; hydrogen bonds; molecular interactions; noncovalent interactions; supramolecular chemistry.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Schematic representation of a) electrostatic interaction, b) charge transfer interactions, c) π‐resonance assistance, d) Pauli (steric) repulsion, e) dispersion, f) cooperativity and g) secondary electrostatic interactions. Adapted with permission from ref. 10. Copyright 2019, ACS.
Figure 2
Figure 2
a) GC and πκ‐base pairs with their monomeric dipole moments in italic [in Debye]; b) Mutual alignment of monomeric dipole moments in GG1 and GG4. Data were taken from ref. 23 and 24.
Figure 3
Figure 3
The π‐resonance in RIHB makes the H acceptor more positive and H donor more negative, which opposes the favorable π‐charge flow in RAHBs.
Figure 4
Figure 4
Atomic charge rearrangement ΔQ (in milli‐electrons) upon HB formation in GC (left) and AT (right) in the σ (up) and π (down) electron systems. Data were taken from ref. 56.
Figure 5
Figure 5
Guanine (G) and xanthine (X) monomers (left) and quartets (right). The purple and orange arrows represent the direction of σ charge flow due to HB formation, and explain why there is a favorable charge separation in G4.
Figure 6
Figure 6
The lone pair on N has a better alignment with the opposing H−N bond, which results in a larger Pauli repulsion for CC than for GG.73
Figure 7
Figure 7
The HB interaction energy becomes stronger when going to bulkier dimers.76
Figure 8
Figure 8
When the HB donors and acceptor are grouped (as in DDAA), there is a larger monomeric charge accumulation than in systems with alternating donors and acceptors (as in DADA), which results in stronger HBs.10
See this image and copyright information in PMC

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